JPH0717854B2 - Spiro bichroman compound and dyeing or printing method using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a material containing a hydroxy group and / or a carbonamide group, particularly cellulose fiber, natural or synthetic polyamide fiber, polyurethane fiber or leather, or a mixed fiber thereof. The present invention relates to a compound useful for dyeing and printing and its application.

<Prior Art> The conventional dyes are still not sufficient in view of the high demands for various fastnesses due to the recent trend toward higher grades, and further leveling up is desired.

<Problems to be Solved by the Invention> Various fastnesses of dyeing or printing of a hydroxy group- and / or carbonamide group-containing material, particularly light fastness and sweat light fastness, are still present especially in the case of hydroxy group-containing fibers. The present invention was not at a sufficiently satisfactory level, and the present inventors diligently made efforts to improve this level, and found out a spirobichroman derivative capable of solving the above problems.

<Means for Solving Problems> The present invention relates to an organic dye residue and the following formula (1). And a method of dyeing or printing a hydroxy group- and / or carbonamido group-containing material, which comprises using at least one compound represented by the formula (1) in the molecule.

The group (1) is a genus of dyes used for the material,
For example, it is possible to design the molecule by incorporating it into an acid dye, a naphthoid dye, a fluorescent dye, a direct dye or a reactive dye, and it is desirable that the incorporation method is via a covalent bond. The linking group with (1) is [In the formula, W represents a bridge member of a hetero ring or a bridge member containing a hetero ring, V represents a hydrogen atom or a lower alkyl group which may have a substituent, and l represents 0 or 1. ] Is advantageous in raw material circumstances, production and performance. W is a linking group that directly constitutes the molecule of the dye, or a group that constitutes the reactive group of the reactive dye that undergoes a nucleophilic substitution reaction with the cellulose fiber, and is a known heterocycle or a crosslinking member containing the same. Above all, a hetero ring containing 2 to 3 nitrogen atoms is preferable. For example,
Examples thereof include a pyridazine ring, a pyrimidine ring, a dioxazine ring and a triazine ring, and a triazine ring is particularly preferable.

Without imparting a fiber-reactive function to the linking group, it may be a compound falling within the category of, for example, an acid dye, a naphthoid dye, a fluorescent dye or a direct dye, or a fiber-reactive function may be added. . The functionalization is performed by using an organic dye residue and / or a heterocycle represented by W and / or
Alternatively, a reactive group known as a reactive group of a reactive dye, for example, a nucleophilic substitution type or a nucleophilic addition type reactive group can be employed.

As a method for assembling the dye molecule by linking the group (1) and the organic dye residue via the linking group, any method according to the method for assembling the triazine-type reactive dye molecule can be adopted.
Among them, the formula [Wherein D is a water-soluble organic dye residue and R is (In the formula, R ′ represents a hydrogen atom or an optionally substituted lower alkyl group. R ₁ and R ₂ are a hydrogen atom, a methyl group, and
A methoxy group, a chlorine atom, a carboxylic acid group, or a sulfonic acid group, and X represents a group —CH═CH ₂ or a group —CH ₂ CH ₂ Y. here,
Y is a group which is eliminated by the action of alkali. Or an aliphatic, aromatic or cyclic amino group having no —SO ₂ X, V is a hydrogen atom or a lower alkyl group which may have a substituent, l is 0 or 1, and n is 1 Or 2 is shown. ] The compound represented by or its salt is suitable.

D is water-soluble, and particularly contains a sulfonic acid group and / or a carboxylic acid group, for example, mono- or poly-azo type, metal complex salt azo type, anthraquinone type, phthalocyanine type, formazan type, azomethine type, dioxazine type , Phenazine-based, stilbene-based, triphenylmethane-based, xanthene-based, thioxanthene-based, nitroaryl-based, naphthoquinone-based, pyrenequinone-based, and perylenecarbimide-based organic dye residues.

Substituents that may be present in the organic dye residue D include the followings in addition to the sulfonic acid group and the carboxylic acid group.

An alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, an alkoxy group having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, acetylamino, An acylamino group having 1 to 8 carbon atoms such as propionylamino, benzoylamino,
Alkylamino groups having 1 to 4 carbon atoms, such as methylamino, ethylamino, propylamino, isopropylamino or butylamino, phenylamino, N,
N-di-β-hydroxyethylamino, N, N-di-β-sulfatoethylamino, sulfobenzylamino, N, N-
Alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy group such as disulfobenzylamino, methoxycarbonyl or ethoxycarbonyl, alkylsulfonyl having 1 to 4 carbon atoms such as methylsulfonyl or ethylsulfonyl, trifluoromethyl ,
Halogen such as nitro, cyano, fluorine, chlorine, bromine,
N-alkylcarbamoyl having 1 to 4 carbon atoms in the alkyl group such as carbamoyl, N-methylcarbamoyl or N-ethylcarbamoyl, sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N-propyl N-alkylsulfamoyl having 1 to 4 carbon atoms such as sulfamoyl, N-isopropylsulfamoyl or N-butylsulfamoyl, N- (β-hydroxyethyl) -sulfamoyl, N, N -Di- (β-hydroxyethyl) -sulfamoyl, ureido, hydroxyl or sulfomethyl.

Among them, particularly preferable substituents are methyl, ethyl, methoxy, ethoxy, acetylamino, benzoylamino, amino, chlorine, bromine, ureido, hydroxyl and sulfomethyl.

Examples of the lower alkyl group which may have a substituent represented by V in the formulas (2) and (3) and R ′ in the formula (4) include, for example, a methyl group, an ethyl group, a propyl group and an isopropyl group. , Butyl group, sec-butyl group, hydroxymethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 8-hydroxypropyl group, 2-hydroxybutyl group, 4-hydroxybutyl group, 1-methyl-2-hydroxy group Propyl group, cyanomethyl group, cyanomethyl group, methoxymethyl group, 2-methoxyethyl group, 8-methoxypropyl group, ethoxymethyl group, 2-ethoxyethyl group, chloromethyl group, 2-chloroethyl group, 8-chloropropyl group, 4-chlorobutyl group, carboxymethyl group, 2-carboxyethyl group, carbamoylmethyl group, 2-carbamoyl group Group, 2-methoxycarbonylethyl group, 2-ethoxycarbonylmethyl group, sulfomethyl group, and a 2-sulfoethyl group.

When X is —CH ₂ CH ₂ Y, Y is a group capable of leaving by the action of calcari, and examples thereof include a sulfate ester group, a thiosulfate ester group, a phosphate ester group, an acetate ester group, and a halogen atom. , Preferred X is —CH═CH ₂ or —CH ₂ CH ₂ O
SO ₃ H.

When the compound of the present invention is present in the form of a free acid or a salt thereof, particularly an alkali metal salt and an alkaline earth metal salt, particularly a sodium salt or a potassium salt is preferable, and when it is used for dyeing and printing a fiber material. Are particularly preferably alkali metal salts.

The spirobichroman compound of the present invention has the formula It can be synthesized by utilizing the reactivity of one of the hydroxyl groups of spirobichroman represented by the formula (1) to bond with an organic dye residue or via a linking group between them.

For more information, [In the formula, V and l have the above-mentioned meanings. ] The organic dye compound having a group represented by the following formula (6) hal-W-hal '(6) [wherein hal and hal' each represent a chlorine atom or a fluorine atom, and W has the above meaning] . ] It synthesize | combines by making a compound represented by these and spirobichroman react sequentially.

More specifically, for example, the compound of formula (3) and its salt can be synthesized as follows.

That is, equation (7) [Wherein D, V, l and n have the above-mentioned meanings. ] In the formula (3), R in the formula (3) is a chlorine atom by condensing at least the same equivalent amount of cyanuric chloride or cyanuric fluoride and at least the same equivalent amount of spirobichroman with an organic dye compound represented by Alternatively, the compound of formula (3) having fluorine atom and its salt can be synthesized.

R is , An aromatic amino group represented by the formula (4) having —SO ₂ X,
Alternatively, the compound of formula (3) which is an aliphatic, aromatic or cyclic amino group having no —SO ₂ X or a salt thereof can be synthesized by condensing the corresponding amine with the compound synthesized above.

In the condensation reaction, the order is not limited to the order described above, but it is preferable that the compounds having low reactivity with cyanuric chloride or cyanuric fluoride are sequentially reacted, and the conditions at that time are the stability of the compound and the stability of the compound. It can be appropriately determined depending on the reactivity, the primary condensation is relatively low,
A pH range and / or a relatively low temperature can be selected, and a relatively high pH range and temperature can be selected as the secondary and tertiary condensations are extended.

Examples of the compound represented by the formula (7) include the following organic dye compounds.

Metal complex salt of dye of the following formula: The metal atom is C _u (1: 1-complex) or C _r and C
_o (1: 2-complex) is preferred. The _Cr- and _Co -complexes may contain one or two azo compounds of the formula given above.
That is, it may be a symmetrical structure, or an asymmetrical structure with any other member.

In this case, Pc means a Cu- or Ni-phthalocyanine group, and the total number of substituents present in the Pc- skeleton is 3 or 4.

In each of the above formulas, the groups R _{5 to} R ₁₀ and R _{17 to} R ₂₀ mean hydrogen or a lower alkyl group, and R ₃ , R ₄ and R _{11 to} R ₁₆ are hydrogen, lower alkyl, alkoxy, alkanoyl. Means amino, ureido, or halogen. The groups R ₃ and R ₄ which belong to the same formula have the above meanings independently of each other. Preferably, the groups R _{5 to} R ₁₀ and R _{17 to} R
₂₀ is hydrogen, methyl or ethyl, and the radicals R ₃ , R ₄ and
R _{11 to} R ₁₆ mean hydrogen, methyl, ethyl, methoxy, ethoxy, acetylamino, ureido or chlorine. The aromatic ring in the above organic dye compound may be optionally further substituted. That is, the benzene ring may be substituted, in particular by methyl, methoxy, ethoxy, carboxyl, acetylamino or chlorine, and the naphthalene ring may be substituted, in particular by methoxy, carboxyl, acetylamino, nitro or chlorine. The same applies to anthraquinones, dioxazines and the like. If it is preferred that the benzene is not further substituted,
Especially as the diazo component, 1,3-phenylenediamine-4
-Sulfonic acid, 1,4-phenylenediamine-2-sulfonic acid, 1,4-phenylenediamine-2,5-disulfonic acid or 1,3-phenylenediamine-4,6-disulfonic acid are used.

Among the compounds represented by the formula (7), particularly preferred are the following formulas [In the formula, A ₁ and A ₂ are each independently a benzene ring or a naphthalene ring which may have a substituent, m ₁ and m ₂ are each independently an integer of 0 to 3, and l is the above-mentioned meaning. Have. ] The bisazo compound shown by these can be mentioned. When a sulfonic acid group is bonded to A ₁ and / or A ₂ in the above formula (m ₁ ≠ 0 and / or m ₂ ≠ 0), the at least one sulfonic acid group is bonded to the adjacent position of each azo group. Preferably.

Among the organic dye compounds represented by the formula (7), specific examples of compounds that can be used as a diazo component and a coupling component for producing an azo organic dye compound are as follows.

<Diazo component> Aminobenzene, 1-amino-2-, -3- or -4
-Methylbenzene, 1-amino-2-, -3- or-
4-methoxybenzene, 1-amino-2-, -3- or -4-chlorobenzene, 1-amino-2,5-dichlorobenzene, 1-amino-2,5-dimethylbenzene, 1-
Amino-3-methyl-6-methoxybenzene, 1-amino-2-methoxy-4-nitrobenzene, 4-aminobiphenyl, 1-aminobenzene-2-, -3- or-
4-carboxylic acid, 2-aminodiphenyl ether, 1-
Aminobenzene-2-, -3- or -4-sulfonic acid amide, -N-methylamide, -N-ethylamide,-
N, N-dimethylamide or -N, N-diethylamide, dehydrothio-p-toluidine-sulfonic acid, 1-amino-3-trifluoromethyl-6-sulfonic acid, 1-amino-3- or -4-nitrobenzene, 1-amino-3
-Or-4-acetylaminobenzene, 1-aminobenzene-2-,-3- or-4-sulfonic acid, 1-aminobenzene-2,4- and -2,5-disulfonic acid, 1-
Amino-4-methylbenzene-2-sulfonic acid, 1-amino-3-methylbenzene-6-sulfonic acid, 1-amino-6-methylbenzene-3- or -4-sulfonic acid, 1-amino-2- Carboxybenzene-4-sulfonic acid, 1-amino-4-carboxybenzene-2-sulfonic acid, 1-amino-4- or -5-chlorobenzene-2-sulfonic acid, 1-amino-6-chlorobenzene-
3- or -4-sulfonic acid, 1-amino-3,4-dichlorobenzene-6-sulfonic acid, 1-amino-2,5-dichlorobenzene-6-sulfonic acid, 1-amino-2,5-
Dichlorobenzene-4-sulfonic acid, 1-amino-4-
Methyl-5-chlorobenzene-2-sulfonic acid, 1-amino-5-methyl-4-chlorobenzene-2-sulfonic acid, 1-amino-4- or -5-methoxybenzene-
2-sulfonic acid, 1-amino-6-methoxybenzene-
3- or -4-sulfonic acid, 1-amino-6-ethoxybenzene-3- or -4-sulfonic acid, 1-amino-2,4-dimethoxybenzene-6-sulfonic acid, 1-amino-2,5 -Dimethoxybenzene-4-sulfonic acid, 1
-Amino-3-acetylaminobenzene-6-sulfonic acid, 1-amino-4-acetylaminobenzene-2-sulfonic acid, 1-amino-3-acetylamino-4-methylbenzene-6-sulfonic acid, 2- Amino-1-methylbenzene-3,5-disulfonic acid, 1-amino-4-methoxybenzene-2,5-disulfonic acid, 1-amino-3-
Or -4-nitrobenzene-6-sulfonic acid, 1-aminonaphthalene, 2-aminonaphthalene, 1-aminonaphthalene-2-,-4-,-5-,-6-,-7-, or -8-sulfone Acid, 2-aminonaphthalene-1-,
-3-, -4-, -5, -6, -7 or -8-
Sulfonic acid, 2-aminonaphthalene-3,6- or -5,7
-Disulfonic acid, 1-aminonaphthalene-3,6- or -5,7-disulfonic acid, 2-aminonaphthalene-1,5-,
-1,7-, -3,6-, -5,7-, -4,8-, or -6,8-
Disulfonic acid, 1-aminonaphthalene-2,5,7-trisulfonic acid, 2-aminonaphthalene-1,5,7-, -3,6,8
-Or -4,6,8-trisulfonic acid, 1-hydroxy-2-aminobenzene-4-sulfonic acid, 1-hydroxy-2-aminobenzene-5-sulfonic acid, 1-hydroxy-2-aminobenzene -4,6-disulfonic acid, 1-
Hydroxy-2-amino-4-acetylaminobenzene-6-sulfonic acid, 1-hydroxy-2-amino-6-
Acetylaminobenzene-4-sulfonic acid, 1-hydroxy-2-amino-4-chlorobenzene-5-sulfonic acid, 1-hydroxy-2-amino-4-methylsulfonylbenzene, 1-amino-2-hydroxy-6- Nitronaphthalene-4-sulfonic acid, 2-amino-1-hydroxynaphthalene-4,8-disulfonic acid, 4-aminoazobenzene-3,4'-disulfonic acid, 3-methoxy-4-
Amino-6-methylazobenzene-2 ', 4'-disulfonic acid, 3-methoxy-4-amino-6-methylazobenzene-2,5'-disulfonic acid, 1,3-diaminobenzene, 1,4-diaminobenzene , 1,3-diamino-4-chlorobenzene, 1,3-diamino-4-methylbenzene, 1,3
-Diamino-4-ethylbenzene, 1,3-diamino-4
-Methoxybenzene, 1,3-diamino-4-ethoxybenzene, 1,4-diamino-2-methylbenzene, 1,4-diamino-2-methoxybenzene, 1,4-diamino-2-
Ethoxybenzene, 1,4-diamino-2-chlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,5-diethylbenzene, 1,4-diamino-2-
Methyl-5-methoxybenzene, 1,4-diamino-2,5-
Dimethoxybenzene, 1,4-diamino-2,5-diethoxybenzene, 2,6-diamino-naphthalene, 1,3-diamino-2,4,6-trimethylbenzene, 1,4-diamino-2,3, Five,
6-tetramethylbenzene, 1,3-diamino-4-nitrobenzene, 4,4'-diaminostilbene, 4,4'-diaminodiphenylmethane, 4,4'-diaminobiphenyl (benzidine), 3,3'-dimethylbenzidine , 3,3′-dimethoxybenzidine, 3,3′-dichlorobenzidine, 3,3 ′
-Dicarboxybenzidine, 3,3'-dicarboxy-methoxy-benzidine, 2,2'-dimethylbenzidine, 4,
2'-diaminodiphenyl (diphenylene), 2,6-diaminonaphthalene-4,8-disulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, 1,4-diaminobenzene-2,5
-Disulfonic acid, 1,4-diaminobenzene-2,6-disulfonic acid, 1,3-diaminobenzene-4-sulfonic acid, 1,3
-Diaminobenzene-4,6-disulfonic acid, 1,4-diamino-2-chlorobenzene-5-sulfonic acid, 1,4-diamino-2-methylbenzene-5-sulfonic acid, 1,5-diamino-6- Methylbenzene-3-sulfonic acid, 1,3-
Diamino-6-methylbenzene-4-sulfonic acid, 3-
(3'- or 4'-aminobenzoylamino) -1-
Aminobenzene-6-sulfonic acid, 1- (4'-aminobenzoylamino) -4-aminobenzene-2,5-disulfonic acid, 1,4-diaminobenzene-2-carboxylic acid,
1,3-diaminobenzene-4-carboxylic acid, 1,2-diaminobenzene-4-carboxylic acid, 1,3-diaminobenzene-5-carboxylic acid, 4,4'-diaminodiphenyl oxide, 4,4'- Diaminophenylurea-2,2'-disulfonic acid, 4,4'-diaminodiphenyloxyethane-2,2'-
Disulfonic acid, 4,4'-diaminostilbene-2,2'-disulfonic acid, 4,4'-diaminodiphenylethane-2,2 '
-Disulfonic acid, 2-amino-5-aminomethylnaphthalene-1-sulfonic acid, 2-amino-5-aminomethylnaphthalene-1,7-disulfonic acid, 1-amino-4-methoxy-5-aminomethylbenzene- 6-sulfonic acid.

When an amino-acetyl compound whose acetyl group is later eliminated by saponification is used as the diazo component instead of the diamine, a monoacetyl compound of the diazo component exemplified above, for example, 1-acetylamino-
3-aminobenzene-4-sulfonic acid or 1-acetylamino-4-aminobenzene-3-sulfonic acid, 1
-Acetylamino-3-amino-6-methylbenzene-
4-sulfonic acid, 2-amino-5-acetylaminomethylnaphthalene-1-sulfonic acid come into consideration.

<Coupling component> Phenol, 1-hydroxy-3- or -4-methylbenzene, 1-hydroxybenzene-4-sulfonic acid,
1-hydroxynaphthalene, 2-hydroxynaphthalene, 2-hydroxynaphthalene-6- or -7-sulfonic acid, 2-hydroxynaphthalene-3,6-or -6,8
-Disulfonic acid, 1-hydroxynaphthalene-4-sulfonic acid, 1-hydroxynaphthalene-4,6-or -4,7
-Disulfonic acid, 1-amino-3-methylbenzene, 1
-Amino-2-methoxy-5-methylbenzene, 1-amino-2,5-dimethylbenzene, 3-aminophenylurea, 1-amino-3-acetylaminobenzene, 1-amino-3-hydroxyacetylaminobenzene, 1,3-
Diaminobenzene-4-sulfonic acid, 1-aminonaphthalene-6- or -8-sulfonic acid, 1-amino-2-
Methoxynaphthalene-6-sulfonic acid, 2-aminonaphthalene-5,7-disulfonic acid, 1-amino-8-hydroxynaphthalene-4-sulfonic acid, 1-amino-8-hydroxynaphthalene-6-sulfonic acid, 1- Amino-8
-Hydroxynaphthalene-2,4-disulfonic acid, 2-hydroxy-3-aminonaphthalene-5,7-disulfonic acid, 1-amino-8-hydroxynaphthalene-2,4,6-
Trisulfonic acid, 1-hydroxy-8-acetylaminonaphthalene-3-sulfonic acid, 1-benzoylamino-
8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 2-benzoylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 2-methyl -Or 2-Ethylamino-5-hydroxynaphthalene-7-sulfonic acid, 2- (N-acetyl-N-methylamino) -5-hydroxynaphthalene-7-sulfonic acid, 2-acetylamino-5-hydroxynaphthalene- 7-sulfonic acid, 2
-Amino-5-hydroxynaphthalene-1,7-disulfonic acid, 2-amino-8-hydroxynaphthalene-6-sulfonic acid, 2-methyl- or -ethylamino-8-hydroxynaphthalene-6-sulfonic acid, 2- (N-Acetyl-N-methylamino) -8-hydroxynaphthalene-6-sulfonic acid, 2-acetylamino-8-hydroxynaphthalene-6-sulfonic acid, 2-amino-8-hydroxynaphthalene-3,6-disulfone Acid, 2-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid, 1-amino-5-hydroxynaphthalene-7-sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6
-Or -4,6-disulfonic acid, 1-acetylamino-
8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 1- (4'-aminobenzoylamino) -8-
Hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 1- (4'-nitrobenzoylamino) -8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid,
1- (3'-aminobenzoylamino) -8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 1-
(3'-Nitrobenzoylamino) -8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 2-
(4'-amino-3'-sulfophenylamino) -5-
Hydroxynaphthalene-7-sulfonic acid, 3-methylpyrazolone- (5), 1-phenyl-3-methyl-5-pyrazolone, 1- (4'-sulfophenyl) -3-methyl-5-pyrazolone, 1- ( 4'-sulfophenyl) -pyrazolone- (5) -3-carboxylic acid, 1- (3'-aminophenyl) -3-methyl-5-pyrazolone, 1-
(2 ', 5'-Disulfophenyl) -3-methyl-5-pyrazolone, 1- (2'-methyl-4'-sulfophenyl) -5-pyrazolone-3-carboxylic acid, 1- (4',
8'-disulfonaphthyl- [2 '])-3-methyl-5
-Pyrazolone, 1- (5 ', 7'-disulfonaphthyl-
[2 '])-3-Methyl-5-pyrazolone, 1-
(2 ', 5'-Dichloro-4'-sulfophenyl) -3-
Methyl-5-pyrazolone, 3-aminocarbonyl-4-
Methyl-6-hydroxypyridone- (2), 1-ethyl-3-cyano- or -3-chloro-4-methyl-6-
Hydroxypyridone- (2), 1-ethyl-3-sulfomethyl-4-methyl-6-hydroxypyridone-
(2), 2,4,6-triamino-3-cyanopyridine, 2-
(3'-Sulfophenylamino) -4,6-diamino-3
-Cyanopyridine, 2- (2'-hydroxyethylamino) -3-cyano-4-methyl-6-aminopyridine,
2,6-bis- (2'-hydroxyethylamino) -3-
Cyano-4-methylpyridine, 1-ethyl-3-carbamoyl-4-methyl-6-hydroxypyridone-
(2), 1-ethyl-3-sulfomethyl-4-methyl-
5-carbamoyl-6-hydroxypyridone- (2),
N-acetoacetylaminobenzene, 1- (N-acetoacetylamino) -2-methoxybenzene-5-sulfonic acid, 4-hydroxyquinolone- (2), 1-amino-
8-hydroxy-2- (phenylazo) -naphthalene-
3,6-disulfonic acid, 1-amino-8-hydroxy-2
-(4'-Sulfophenylazo) -naphthalene-3,6-
Disulfonic acid, 1-amino-8-hydroxy-2-
(2 ', 5'-disulfophenylazo) -naphthalene-3,
6-disulfonic acid, 1-β-aminoethyl-3-cyano-4-methyl-6-hydroxypyridone- (2), 1-
γ-aminopropyl-3-sulfomethyl-4-methyl-
6-hydroxypyridone- (2), 1,3-diaminobenzene, 1-amino-3-N, N-di-β-hydroxyethylaminobenzene, 1-amino-3-N, N-di-β-sulfur Fatoethylaminobenzene, 1-amino-3-N, N
-Di-β-hydroxyethylamino-4-methoxybenzene, 1-amino-3-N, N-di-β-sulfato-ethylamino-4-methoxybenzene, 1-amino-3-
Sulfo-benzylamino-benzene, 1-amino-3-
Sulfo-benzylamino-4-chlorobenzene, 1-amino-3-N, N-disulfo-benzylaminobenzene.

The compound of the present invention is a very good dyed product by dyeing or printing a hydroxy group- and / or carbonamide group-containing material, particularly cellulose fiber, natural or synthetic polyamide fiber, polyurethane fiber or leather, or a blended fiber thereof. give. As the method, a usual dyeing or printing method in the dye field of the genus to which each of the compounds of the present invention belongs can be applied. Among them, the compound of the present invention, which is a reactive dye, is particularly useful for cellulose fibers,
It is carried out as follows.

That is, in the case of the exhaust method, sodium carbonate, sodium tertiary phosphate,
It is carried out at a relatively low temperature in a dyebath containing sodium sulfate or salt in the presence of an acid binder such as caustic soda. It can also be dyed by a printing method, for example, an acid binder such as sodium bicarbonate, sodium carbonate, sodium phosphate tribasic, caustic soda, etc. and a paste containing urea and a paste, preferably sodium alginate, etc. It is carried out by steaming or dry heating at 100 to 200 ° C.

The compound of the present invention is characterized in that it exhibits excellent performance by dyeing or printing a hydroxy group- and / or carbonamide group-containing material. Among them, it is suitable for cellulose fibers, the obtained dyed product or printed product is thick and excellent in levelness, and is good in general fastness, among which light fastness, sweat and sweat light fastness The degree is excellent. When the compound of the present invention is a reactive dye, in addition to the above characteristics, it has further excellent reactivity and fixing property, and in the case of the exhaust method, it can be used at a relatively low temperature.

Next, the present invention will be described with reference to examples.

In the text, parts represent parts by weight.

Example 1 16.8 parts of aniline-4-sulfonic acid and 2 parts of concentrated hydrochloric acid in 75 parts of ice water
Add 2.6 parts, and add 35% sodium nitrite solution 19.6 at 0-5 ° C.
Part is injected to perform diazotization. After removing excess nitrous acid, 1-amino-8-hydroxynaphthalene-3,6-
Disulfonic acid monosodium salt 30.1 parts neutral solution 0 to
Coupling is performed by injecting at 10 ° C. in about 1 hour.
The mixture is stirred for several hours to obtain a solution of monoazo compound.

Then 1-acetylamino-3-aminobenzene-4-
21.6 parts of sulfonic acid was diazotized, and this was injected into a monoazo dye solution adjusted to pH 6.0 to 6.5 at 5 to 10 ° C for coupling. After stirring for 1 to 2 hours, caustic soda is added to make the mixture alkaline, and the mixture is heated to 80 to 90 ° C. to hydrolyze the acetyl group. After neutralization, salting out with sodium chloride gives 40 parts of the disazo compound having the following structure in the form of a free acid.

This disazo compound and 11 parts of cyanuric chloride were subjected to a first condensation by keeping the pH at 3 to 4 in 300 parts of an aqueous solution of a surfactant for 1 to 2 hours at 0 to 5 ° C., followed by spirobichroman 1
A second condensation is carried out by adding 9.3 parts and stirring overnight at 25-30 ° C while maintaining pH 8-9. PH 5 with dilute hydrochloric acid
~ 6, salted out with sodium chloride, washed, dried, and free acid in the form of a spirobichroman compound of the following structure 55
I got a part.

Example 2 A spirobichroman compound consisting of the following diazo components B and C and azo component A was synthesized in the same manner as in Example 1.

These compounds are characterized by the azo component: column A, the diazo component of the monoazo compound: column B, the diazo component of the disazo compound: column C, and the color tone of the disazo compound on the cellulose fiber: column D.

Example 3 Each spirobichroman compound shown in Examples 1-2
0.3 part is dissolved in 200 parts of water, 10 parts of Glauber's salt is added, 10 parts of cotton is added, and the temperature is raised to 50 ° C. Then, after 20 minutes, add 4 parts of sodium carbonate.

Dye at that temperature for 1 hour. After the completion of dyeing, the product was washed with water and soaped to obtain a navy dyed product which was excellent in sweat, light resistance and sweat light fastness.

Example 4 11 parts of the spirobichroman compound obtained in Example 1 was dissolved in 150 parts of water, and 1-aminobenzene-3 was added thereto.
Add 2.7 parts of -β-sulfatoethyl sulfone to adjust the pH to
4. Stir for 10 hours while controlling the temperature at 80-100 ° C.
After completion of the reaction, the mixture was cooled to room temperature and then salted out with sodium chloride to obtain a spirobichroman compound having the following structure in the form of a free acid.

Example 5 Synthesis was carried out by performing the third condensation in the same manner as in Example 4 except that the following amine component was used instead of 1-aminobenzene-3-β-sulfatoethylsulfone.

The third condensed amine component is shown in Column A, and the color tone of the obtained spirobichroman compound on cellulose fiber is shown in Column B.

Example 6 In Example 1 and 2, it carried out by the same method except having used cyanuric fluoride instead of cyanuric chloride, and obtained the corresponding spirobichroman compound. These were dyed by the method of Example 8 and likewise showed excellent performance.

Example 7 The spirobichroman compound synthesized in Example 2 is condensed with the third condensed amine component used in Examples 4 and 5 in the same manner to dye in a navy color excellent in sweat, light resistance and sweat light resistance. A spirobichroman compound giving a product was obtained.

Example 8 1-Amino-4- (3'-amino-2 ', 4', 6'-trimethylphenylamino) -anthraquinone-2,5'-disulfonic acid 25.6 parts to a neutral aqueous solution in 200 parts water. Add 9.2 parts of cyanuric chloride and adjust the pH to 3-4 at 0-5 ℃.
Stir for hours. Then add spirobichroman 18.8 to this solution.
Parts are added and the second condensation is carried out by stirring overnight at 25-30 ° C. while maintaining pH 8-9. PH 5 ~ with dilute hydrochloric acid
No. 6, salted out with sodium chloride, separated and dried by aeration,
A dye of the following structure was obtained in the form of the free acid.

Example 9 A dye could likewise be obtained by condensing the amino dye compound listed in column 2 of the following table with an equivalent amount of cyanuric chloride followed by spirobichroman as described in Example 8.

Example 10 1-Amino-8-hydroxynaphthalene-3,6-disulfonic acid (6.4 parts) was added to 50 parts of water, and while adjusting to 0 to 20 ° C. and pH 1 to 3, 3.7 parts of cyanuric chloride was added at the same temperature, Free 1-amino-8-hydroxynaphthalene-3,6-at the same pH
After stirring until no disulfonic acid is observed, 6.8 parts of spirobichroman is subsequently added, and the mixture is stirred overnight at 25 to 30 ° C. while maintaining pH 8 to 9 to perform the second condensation. 2-Aminonaphthalene-diazotized into this reaction solution by a known method
Add 6.1 parts of 1,5-disulfonic acid, pH 4-5, temperature 0-10
Coupling was performed at ° C. After completion of the reaction, salting out with sodium chloride was carried out to obtain a dye having the following structure in the form of free acid.

Example 11 4.8 parts of 2-amino-5-hydroxynaphthalene-7-sulfonic acid was added to 50 parts of water, and 3.7 parts of cyanuric chloride was added while adjusting the pH to 0 to 20 ° C. and pH 1 to 3, at the same temperature and pH. Stir until no free 2-amino-5-hydroxynaphthalene-7-sulfonic acid is visible. 4-Methoxyaniline-2, which was diazotized to this reaction solution by a known method,
-4.1 parts of sulfonic acid was added and coupling was carried out at pH 4-5 and temperature 0-10 ° C. Spirobichroman was added to this reaction mixture.
Add 4.7 parts and stir overnight at 25-30 ° C while maintaining pH 8-9. After completion of the reaction, salting out with potassium chloride was carried out to obtain a dye having the following structure in the form of free acid.

Example 12 Each of the spirobichroman compounds obtained in Examples 4, 5 and 8 to 11 was used as a reactive dye, and dyed by the method of Example 3 to obtain a dyed product having similarly excellent performance. .

Example 13 According to Examples 10 and 11, cyanuric chloride and second in the table on the next page
Dyes were similarly obtained by reacting with the coupling components listed in the column, followed by reaction with spirobichroman and coupling reaction with the diazo component in the third column in any order.

Example 14 19 parts of a stilbene compound represented by the following formula is neutrally dissolved in 150 parts of water.

To this solution, add 19 parts of cyanuric chloride, 0-20 ° C, pH 1-
While adjusting to 3, the mixture is stirred at the same temperature and the same pH until no free stilbene compound is observed. Next, add 35 parts of spirobichroman, and maintain at pH 8-9, 25-30 ℃
A second condensation is carried out by stirring overnight at. To this solution is added 6.3 parts of monoethanolamine, and the mixture is stirred at 70 to 90 ° C to carry out the third condensation. After completion of the reaction, acid precipitation was performed to obtain the following dye in the form of free acid.

Example 15 Using the stilbene compound shown in Example 14, cyanuric chloride and spirobichroman were sequentially condensed in the same manner, and a dye was synthesized using the following compound as the amine component required for the third condensation reaction. .

Example 16 As a result of dyeing the cellulosic fibers with the compounds obtained in Examples 14 and 15 as a fluorescent dye, excellent whitening property and excellent fastness were exhibited.

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Claims (4)

[Claims] 1. The following formula (3): [Wherein D is a water-soluble organic dye residue, R is a fluorine atom, a chlorine atom, (In the formula, R'represents a hydrogen atom or an optionally substituted lower alkyl group. R ₁ and R ₂ are each independently a hydrogen atom, a methyl group, a methoxy group, a chlorine atom, a carboxylic acid group or a sulfonic acid group, X represents a group —CH═CH ₂ or a group —CH ₂ CH ₂ Y, where Y is a group capable of leaving by the action of an alkali), β-hydroxyethylamino, bis (β-hydroxyethyl) ) Amino, β-sulfoethylamino, phenylamino or a morpholino group is shown, V is a hydrogen atom or a lower alkyl group which may have a substituent, l is 0 or 1,
n represents 1 or 2. ] The spirobichroman compound or its salt represented by these. 2. D is [In the formula, A ₁ and A ₂ are each independently a benzene ring or a naphthalene ring which may have a substituent, and m ₁ and m ₂ are each independently an integer of 0 to 3. ] The compound or its salt according to claim 1, which is a water-soluble organic dye residue represented by: 3. _One of the sulfonic acid groups bound to A ₁ is bound to the adjacent position of the azo group constituting D, and / or one of the sulfonic acid groups bound to A ₂ constitutes D. The compound or a salt thereof according to claim 2, which is bonded to the adjacent position of another azo group. 4. The following formula (3) [Wherein D is a water-soluble organic dye residue, R is a fluorine atom, a chlorine atom, (In the formula, R'represents a hydrogen atom or an optionally substituted lower alkyl group. R ₁ and R ₂ are each independently a hydrogen atom, a methyl group, a methoxy group, a chlorine atom, a carboxylic acid group or a sulfonic acid group, X represents a group —CH═CH ₂ or a group —CH ₂ CH ₂ Y, where Y is a group capable of leaving by the action of an alkali), β-hydroxyethylamino, bis (β-hydroxyethyl) ) Amino, β-sulfoethylamino, phenylamino or a morpholino group is shown, V is a hydrogen atom or a lower alkyl group which may have a substituent, l is 0 or 1,
n represents 1 or 2. ] A method for dyeing or printing a hydroxy group- and / or carbonamide group-containing material, characterized by using a spirobichroman compound represented by